CN114409966A - Waste glass fiber recycling and granulating method and application thereof - Google Patents
Waste glass fiber recycling and granulating method and application thereof Download PDFInfo
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
- C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
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- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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Abstract
A method for recovering and granulating waste glass fibers and application thereof are disclosed, wherein the method comprises the following steps: (1) infiltrating: adding waste glass fiber yarns into the impregnating agent solution, and heating and impregnating to obtain impregnated glass fibers; (2) cutting and grinding: cutting short the infiltrated glass fiber obtained in the step (1), and grinding to obtain glass fiber powder; (3) granulating and drying: and (3) extruding and molding the glass fiber powder obtained in the step (2), and carrying out granulation, drying and packaging to obtain glass fiber particles. The glass fiber particles obtained by the waste glass fiber recycling and granulating method replace the certified glass fibers and are used as the reinforcing modifier for reinforced nylon, reinforced PP or reinforced PBT materials. The quality of the glass fiber particles obtained by the method is close to the level of certified glass fibers, the glass fiber particles have a good reinforcing effect on nylon, PP or PBT materials, the waste utilization rate is high, the method is green and environment-friendly, the process is simple, the cost is low, and the method is suitable for industrial production.
Description
Technical Field
The invention relates to a glass fiber granulation method and application thereof, in particular to a waste glass fiber recovery granulation method and application thereof.
Background
The glass fiber is widely applied to the reinforced modified material of the thermoplastic engineering plastic as a reinforced material. Glass fiber materials in China are produced to 300 ten thousand tons per year, corresponding waste glass fiber yarns are produced to 6-10 ten thousand tons per year, most of the waste glass fibers are used as garbage to be buried, and a small part of the waste glass fibers are recycled and woven into glass fiber cloth to be used in rural septic tanks recently. The waste glass fiber yarns are various in variety, the diameters of the monofilaments are 11-18 mm, the monofilaments are different in length, and the waste glass fiber yarns are not formed into tows and are difficult to recycle and process and only can be discarded. Therefore, the problem of recycling the waste fiber yarn is a difficult problem which troubles the domestic glass fiber enterprises.
CN109382233A discloses a waste glass fiber excess material spray drying device and a method, which are mainly used for a waste glass fiber surface treating agent drying device, and are only one procedure and device in the waste glass fiber recovery process. The waste glass fiber yarn treated by the method can be only used for low-end applications such as glass fiber reinforced plastics and the like, but can not be used for reinforcing modified engineering plastics.
In conclusion, a method for recycling waste glass fibers is lacked in the prior art, and a method for recycling and granulating waste glass fibers, which is suitable for industrial production, has the advantages of good reinforcing effect on nylon, PP or PBT materials, high waste utilization rate, environmental friendliness, simple process and low cost and is close to the quality of the fine glass particles.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and providing the method for recycling and granulating the waste glass fiber and the application thereof, wherein the quality of the obtained glass fiber particles is close to the level of the certified glass fiber, the method has good reinforcing effect on nylon, PP or PBT materials, high waste utilization rate, environmental protection, simple process and low cost, and is suitable for industrial production.
The technical scheme adopted by the invention for solving the technical problems is as follows: a method for recovering and granulating waste glass fibers comprises the following steps:
(1) infiltrating: adding the waste glass fiber yarn into the impregnating compound solution, and heating and impregnating to obtain an impregnated glass fiber yarn;
(2) cutting and grinding: cutting short the infiltrated glass fiber obtained in the step (1), and grinding to obtain glass fiber powder;
(3) granulating and drying: and (3) extruding and molding the glass fiber powder obtained in the step (2), and carrying out granulation, drying and packaging to obtain glass fiber particles.
Preferably, in the step (1), the waste glass fibers are unqualified products or transition products generated in the glass fiber production process due to process adjustment or product specification adjustment, and comprise mixtures of various glass fiber yarns with different monofilament diameters and different lengths.
Preferably, in the step (1), the mass ratio of the waste glass fibers to the impregnating compound solution is 100: 40-80. The amount of the impregnating compound has great influence on the binding force between glass fiber yarns and between glass fibers and resin during subsequent modification, if the amount of the impregnating compound is too small, the glass fiber yarns have poor bundling property, a large amount of powder or single yarns are generated in the grinding and extruding process, and the forming and granulation of the glass fiber yarns are seriously influenced; if the amount of the impregnating agent is too large, the production cost increases.
Preferably, in the step (1), the impregnating agent solution comprises the following components in parts by weight: 100 parts of water, 20-40 parts (more preferably 30-40 parts) of a binder, 5-10 parts (more preferably 8-10 parts) of an emulsifier, and 2-6 parts (more preferably 4-6 parts) of a coupling agent. In the impregnating compound, because more polar groups exist on the surface of the glass fiber, the steering groups can physically combine with water molecules to form water, and the water serving as an impregnating medium can accelerate the impregnating speed of the auxiliary agent on the glass fiber; the binder can bind the glass fiber yarn monofilaments into tows, the content of the binder is critical to the binding of the glass fiber yarn, when the binder is used in a small amount, the glass fiber yarn is not tightly or even loosely bound, the production of glass fiber yarn particles is not facilitated, particularly, due to poor binding property, the produced glass fiber particles are easy to loose, broken filaments are easily produced in the downstream customer test process, the extrusion and feeding of the glass fiber particles are unstable, and the stable feeding of the glass fiber particles cannot be realized, but when the binder is used in an excessive amount, the production cost is increased, more importantly, the content of the binder is too high, and the mechanical property of the reinforced resin composite material is reduced; the emulsifier is used for dispersing oily compounds such as the binder, the coupling agent and the like into water to form fine particles, so that the uniform and rapid dispersion of the binder and the coupling agent on the surface of the glass fiber yarn is facilitated, the larger the using amount of the emulsifier is, the more uniformly the organic binder and the coupling agent are dispersed, the smaller the particles are, otherwise, the poor dispersion of the organic matter is, but when the using amount of the emulsifier is too large, the binder is completely coated by the emulsifier, so that the bonding strength of the binder to the glass fiber yarn is reduced; the coupling agent mainly has the effect of improving the binding power between the glass fibers and the resin so as to improve the reinforcing effect of the glass fibers on the resin, when the using amount of the coupling agent is large, the reinforcing effect of the manufactured glass fiber particles is good, otherwise, the reinforcing effect is poor, but when the using amount of the coupling agent is too large, the chemical combination with the glass fiber surface is saturated, and part of the coupling agent which does not react with the glass fiber surface cannot generate the coupling effect and is transferred to the surface of the composite material, so that the surface performance or the mechanical performance of the composite material is influenced.
Preferably, in step (1), the binder comprises one or more of water-soluble epoxy resin, water-soluble polyurethane or polyether amide. The three binders have good solubility with water, good binding force with glass fiber yarns, and certain chemical binding force with polyester and polyamide resin. The binding force of the binding agent, the glass fiber and the resin is considered comprehensively, and the comparison sequence of the binding capacity is as follows: water-soluble polyurethane > water-soluble epoxy resin > polyetheramide, more preferably, the binder is a water-soluble epoxy resin or a water-soluble polyurethane.
Preferably, in step (1), the emulsifier comprises one or more of an anionic emulsifier, a nonionic fatty alcohol polyoxyethylene ether or a polyol type emulsifier. More preferably, the anionic emulsifier comprises one or more of sodium stearate, sodium lauryl sulfate or sodium oleate; the nonionic fatty alcohol polyoxyethylether comprises octyl phenol polyoxyethylether (TX-10) and/or nonyl phenol polyoxyethylether (OP-10) and the like; the polyhydric alcohol type emulsifier comprises one or more of ethylene glycol, glycerol pentaerythritol or sorbitan and the like. The emulsification action sequence of the anionic emulsifier, the nonionic fatty alcohol polyoxyethylene ether and the polyol emulsifier on the binder and the coupling agent is as follows: the nonionic fatty alcohol polyoxyethylene ether is larger than the polyalcohol emulsifier is larger than the anionic emulsifier, and more preferably, the emulsifier is nonionic fatty alcohol polyoxyethylene ether or polyalcohol emulsifier.
Preferably, in step (1), the coupling agent includes a silane-based coupling agent and the like. More preferably, the silane coupling agent comprises one or more of KH550, KH560 or KH 570. Selecting the variety of the coupling agent in consideration of the emulsibility and the dispersibility of the coupling agent, and combining the viscosity sequence of several coupling agents: KH570 > KH560 > KH550, more preferably the coupling agent is KH 550.
Preferably, in the step (1), the temperature for heating and soaking is 40-80 ℃ and the time is 30-60 min. The glass fiber yarn soaking function is to enable the glass fiber yarn monofilaments to be mutually bonded into bundles, reduce the surface static electricity of the glass fibers, improve the lubricity of the surface of the glass fibers, enhance the cohesiveness between the surface of the glass fibers and polymers, and enable the recycled glass fibers to meet the reinforcing function of the thermoplastic composite material. The higher heating and soaking temperature is more beneficial to improving the soaking effect, but when the heating and soaking temperature is too high, the volatilization of the soaking agent can be caused, when the heating and soaking time is too short, the glass fiber yarns are not fully soaked, the glass fiber bonding and bundling effect is influenced, and when the heating and soaking time is too long, the production efficiency is influenced.
Preferably, in the step (2), the cutting is performed to a length of 3-20 mm.
Preferably, in the step (2), the feeding amount of the grinding is 40-2000 kg/h (more preferably 800-1800 kg/h), the rotation speed of the grinding disc is 40-200 rpm (more preferably 80-180 rpm), and the grinding is carried out until the particle size is 1-5 mm (more preferably 2-4 mm). When the rotating speed of the grinding disc is too fast or the feeding amount is too small, the size of the glass fiber powder is small, when the length of the glass fiber powder is too small, the reinforcing effect is small, and when the rotating speed of the grinding disc is too slow or the feeding amount is too large, the size of the glass fiber powder is too large, the surface of the glass fiber reinforced resin material is rough, and the appearance of the product is influenced.
Preferably, in the step (3), the rotation speed of the extrusion is 60-150 rpm (more preferably 60-100 rpm), and the temperature is 60-250 ℃ (more preferably 100-200 ℃). When the rotating speed of the double-roller extruder is too high, the length of the glass fiber powder is reduced, meanwhile, the friction heat between the glass fiber powder is increased, so that the impregnating compound is volatilized too much, the produced glass fiber particles are loose or not formed, and when the rotating speed is too low, the length of the glass fiber powder is large; too high an extrusion temperature may cause too much volatilization of the sizing agent, resulting in loose or unshaped glass fiber particles, while too low an extrusion temperature may cause incomplete melting of the sizing agent, thereby reducing the extrusion flowability of the fibers.
Preferably, in the step (3), the speed of the granules is 40 to 200rpm (more preferably 80 to 180 rpm). When the granulating speed is low, the glass fiber particle size is large, the surface appearance of the reinforced resin composite material is influenced, and when the granulating speed is too high, powder can be generated.
Preferably, in the step (3), the particle size of the cut pellets is 1 to 10mm (more preferably 2 to 6 mm). When the particle shape is non-spherical, the particle size is an equivalent particle size.
Preferably, in the step (3), the shape of the pelletized glass fiber particles is cylindrical, square, polygonal cylindrical, spherical or irregular particles.
Therefore, it is necessary to design the extrusion and granulation process reasonably.
Preferably, in the step (3), the drying temperature is 100 to 200 ℃ (more preferably 100 to 110 ℃) for 20 to 60min (more preferably 20 to 30 min). The purpose of drying is to remove moisture from the glass fiber particles, which ensures sufficient evaporation of the moisture under the drying conditions.
The technical scheme adopted for further solving the technical problems is as follows: the glass fiber particles obtained by the waste glass fiber recycling and granulating method are used for replacing the certified glass fiber and are used as a reinforcing modifier for reinforced nylon, reinforced PP or reinforced PBT materials.
The method has the following beneficial effects:
(1) the quality of the glass fiber particles obtained by the method is close to the level of the glass fiber of a certified product, the glass fiber particles have a good reinforcing effect on materials such as nylon, reinforced PP (polypropylene) or reinforced PBT (polybutylene terephthalate), and the waste utilization rate is high;
(2) the method reduces the environmental pollution caused by waste discharge in the glass fiber production process, is green and environment-friendly, has simple process and low cost, and is suitable for industrial production;
(3) the glass fiber particles obtained by the method change waste glass fiber yarns which are discarded and buried as garbage for a long time into usable commodities, can be widely used as reinforcing modifiers for reinforced nylon, reinforced PP or reinforced PBT and other materials, and meet the requirements of engineering plastic reinforced materials.
Detailed Description
The present invention will be further described with reference to the following examples.
The waste glass fiber yarns used in the embodiment of the invention are mixtures of glass fiber yarns with different monofilament diameters (including 10mm, 12mm, 14mm, 17mm, 20mm and the like) and different lengths (1-20 m and the like), and are from Chongqing International composite Co., Ltd and Zhejiang Tongxiang Jushi group; the starting materials or chemicals used in the examples of the present invention are, unless otherwise specified, commercially available in a conventional manner.
Reference examples 1 to 5 of treating agent solutions
The components and parts by weight of the impregnating agent solutions in reference examples 1 to 5 and comparative examples 1 and 2 are shown in Table 1.
TABLE 1 Components and parts by weight of impregnating agent solutions reference examples 1-5 and comparative examples 1, 2
Note: in the table, "-" indicates no addition; the formulations of the impregnating agent solutions of examples 3 and 4 were the same as those of example 1; the sizing agent solutions obtained in example 1, example 2, example 5, comparative example 1, and comparative example 2 were referred to as sizing agent solution 1, sizing agent solution 2, sizing agent solution 3, sizing agent solution 4, and sizing agent solution 5 in this order.
Waste glass fiber recovery and granulation method in embodiment 1
(1) Infiltrating: adding 1000kg of waste glass fibers into 600kg of impregnating compound solution 1, and heating and impregnating for 60min at 60 ℃ to obtain impregnated glass fibers;
(2) cutting and grinding: cutting the infiltrated glass fiber obtained in the step (1) to 8mm in length, and grinding the infiltrated glass fiber to 4mm in particle size by a grinding disc machine with the feeding amount of 1500kg/h and the grinding disc rotating speed of 180rpm to obtain glass fiber powder;
(3) granulating and drying: adding the glass fiber powder obtained in the step (2) into a pair-roller extrusion granulator, extruding and molding at the rotating speed of 100rpm and the temperature of 200 ℃, then carrying out surface grinding and granulating at the speed of 180rpm to obtain cylindrical particles with the particle size of 6mm, drying for 30min at the temperature of 110 ℃ by using a fluidized bed dryer, and packaging to obtain the glass fiber particles.
Waste glass fiber recovery and granulation method in embodiment 2
This example differs from example 1 only in that: adding an impregnating agent solution 2 into the step (1). The same as in example 1.
Waste glass fiber recovery and granulation method in embodiment 3
(1) Infiltrating: adding 1000kg of waste glass fibers into 800kg of impregnating compound solution 1, and heating and impregnating for 50min at 50 ℃ to obtain impregnated glass fibers;
(2) cutting and grinding: cutting the infiltrated glass fiber obtained in the step (1) to a length of 10mm, and grinding the infiltrated glass fiber to a particle size of 4mm by a grinding disc machine with a feeding amount of 800kg/h and a grinding disc rotating speed of 100rpm to obtain glass fiber powder;
(3) granulating and drying: and (3) adding the glass fiber powder obtained in the step (2) into a double-roller extrusion granulator, performing extrusion molding at the rotating speed of 60rpm and the temperature of 120 ℃, performing surface grinding and granulation at the speed of 100rpm to obtain square particles with the particle size of 4mm, drying for 20min at the temperature of 100 ℃ by using a fluidized bed dryer, and packaging to obtain the glass fiber particles.
Example 4 of method for recycling and granulating waste glass fibers
(1) Infiltrating: adding 1000kg of waste glass fibers into 800kg of impregnating compound solution 1, and heating and impregnating for 50min at 50 ℃ to obtain impregnated glass fibers;
(2) cutting and grinding: cutting the infiltrated glass fiber obtained in the step (1) to 6mm in length, and grinding the infiltrated glass fiber to 3mm in particle size by a grinding disc machine with the feeding amount of 1000kg/h and the grinding disc rotating speed of 140rpm to obtain glass fiber powder;
(3) granulating and drying: adding the glass fiber powder obtained in the step (2) into a pair-roller extrusion granulator, extruding and molding at the rotating speed of 80rpm and the temperature of 150 ℃, then carrying out flour milling and granulating at the speed of 140rpm to obtain spherical particles with the particle size of 5mm, drying for 20min at the temperature of 100 ℃ by using a fluidized bed dryer, and packaging to obtain the glass fiber particles.
Example 5 of method for recycling and granulating waste glass fibers
This example differs from example 1 only in that: 600kg of impregnating compound solution 3 is added in the step (1). The same as in example 1.
Application examples 1-5 of glass fiber particles obtained by waste glass fiber recycling and granulating method
The glass fiber particles obtained by the waste glass fiber recycling and granulating method in the embodiment 1-5 are used for replacing the certified glass fiber and are used as a reinforcing modifier for reinforced nylon, reinforced PP or reinforced PBT materials.
Comparative examples 1 and 2
Comparative examples 1, 2 differ from example 1 only in that: the compositions of the impregnating agents added in the step (1) are different (as shown in table 1). The same as in example 1.
In order to evaluate the reliability of the impregnating compound formula, the impregnating process and the granulation process used in embodiments 1 to 5 of the method of the present invention:
(1) and (3) detecting the performance of the glass fiber particles:
measuring the powder content in the glass fiber particles, wherein the lower the powder content is, the better the impregnating compound formula and the impregnating and granulating processes are, and the results are shown in table 2;
(2) indirectly characterizing the quality of the recycled glass fiber particles:
the mechanical properties of the reinforced blending composite material of PA6 are compared and evaluated by the glass fiber particles obtained in the embodiments 1-5, the glass fiber particles obtained in the comparative examples 1 and 2 and the certified short glass fiber 301HP (the comparative example 3, which is purchased from Chongqing International composite Co., Ltd.), and the formula of the reinforced blending composite material of PA6 is as follows:
mixing and extruding PA6 (Baling petrochemical YH 800) with the glass fiber particles obtained in the embodiments 1-5, the glass fiber particles obtained in the comparative examples 1 and 2 or the certified short glass fiber 301HP (the content of the glass fiber is 30%), the antioxidants 1098 and 160 and the lubricant silicone according to the existing method to respectively obtain the glass fiber reinforced PA6 composite material;
the detection standard of the mechanical property of the composite material is as follows: tensile strength/MPa: ASTM D638, flexural Strength/MPa: ASTM D790, flexural modulus/MPa: ASTM D790, notched Izod impact strength/kJ/m2: ASTM D756, unnotched impact strength/kJ/m2(ii) a The results are shown in Table 2.
TABLE 2 comparison table of performances of glass fiber particles prepared in examples 1-5 and comparative examples 1-3 and glass fiber reinforced PA6 composite material prepared from the same
As can be seen from table 2, the powder content of the glass fiber particles obtained in embodiments 1 to 5 of the method of the present invention can be controlled to be less than 5%, and the reinforced PA6 composite material has the same reinforcing effect as the certified short glass fiber 301HP, which indicates that the recycled waste glass fiber material obtained by using the method of the present invention has a small influence on the performance of the reinforced PA6 product, and the recycled waste glass fiber material can completely replace the certified glass fiber for the production of the reinforced nylon composite material, as proved by the customer use, the method of the present invention is feasible for the recycling method of the waste glass fiber; the glass fiber particles obtained in the comparison document 1 are powdery due to no addition of the binder, so that the charging is difficult, and the impregnating compound used in the comparison document 2 is not added with the coupling agent, so that the binding force between the surface of the glass fiber and the resin is reduced, and the mechanical property of the prepared composite material is poor. The PA6 composite material has better surface property or mechanical property under the condition of proper dosage of the binder, the emulsifier and the coupling agent.
Claims (6)
1. A method for recovering and granulating waste glass fibers is characterized by comprising the following steps:
(1) infiltrating: adding the waste glass fiber yarn into the impregnating compound solution, and heating and impregnating to obtain an impregnated glass fiber yarn;
(2) cutting and grinding: cutting short the infiltrated glass fiber obtained in the step (1), and grinding to obtain glass fiber powder;
(3) granulating and drying: and (3) extruding and molding the glass fiber powder obtained in the step (2), and carrying out granulation, drying and packaging to obtain glass fiber particles.
2. The method for recycling and granulating waste glass fiber according to claim 1, wherein: in the step (1), the mass ratio of the waste glass fibers to the impregnating compound solution is 100: 40-80; the impregnating compound solution comprises the following components in parts by weight: 100 parts of water, 20-40 parts of a binder, 5-10 parts of an emulsifier and 2-6 parts of a coupling agent; the binder comprises one or more of water-soluble epoxy resin, water-soluble polyurethane or polyether amide; the emulsifier comprises one or more of anionic emulsifier, nonionic fatty alcohol polyoxyethylene ether or polyol emulsifier; the coupling agent comprises a silane coupling agent; the temperature of the heating and soaking is 40-80 ℃, and the time is 30-60 min.
3. The method for recycling and pelletizing waste glass fiber according to claim 1 or 2, characterized in that: in the step (2), cutting to a length of 3-20 mm; the feeding amount of the grinding is 40-2000 kg/h, the rotating speed of the grinding disc is 40-200 rpm, and the grinding is carried out until the grain size is 1-5 mm.
4. The method for recycling and pelletizing waste glass fiber according to claim 1 or 2, characterized in that: in the step (3), the rotating speed of the extrusion is 60-150 rpm, and the temperature is 60-250 ℃; the speed of the grain cutting is 40-200 rpm; the grain size of the cut grains is 1-10 mm; the shape of the glass fiber particles after being cut into granules is cylindrical, square, polygonal cylindrical, spherical or irregular particles; the drying temperature is 100-200 ℃, and the drying time is 20-60 min.
5. The method for recycling and granulating waste glass fiber according to claim 3, wherein: in the step (3), the rotating speed of the extrusion is 60-150 rpm, and the temperature is 60-250 ℃; the speed of the grain cutting is 40-200 rpm; the grain size of the cut grains is 1-10 mm; the shape of the glass fiber particles after being cut into granules is cylindrical, square, polygonal cylindrical, spherical or irregular particles; the drying temperature is 100-200 ℃, and the drying time is 20-60 min.
6. The use of the glass fiber granules obtained by the method for recycling and granulating waste glass fibers as claimed in any one of claims 1 to 5, wherein the method comprises the following steps: the glass fiber particles obtained by the method for recycling and granulating the waste glass fibers in any one of claims 1 to 5 are used as reinforcing modifiers for reinforced nylon, reinforced PP or reinforced PBT materials instead of the certified glass fibers.
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| CN113246426A (en) * | 2021-05-11 | 2021-08-13 | 山东玻纤集团股份有限公司 | Production system and method of glass fiber reinforced composite material |
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| CN108751748A (en) * | 2018-05-28 | 2018-11-06 | 宁波东邦新材料有限公司 | A kind of basalt chopped fiber size |
| CN113246426A (en) * | 2021-05-11 | 2021-08-13 | 山东玻纤集团股份有限公司 | Production system and method of glass fiber reinforced composite material |
| CN113234284A (en) * | 2021-06-10 | 2021-08-10 | 山东玻纤集团股份有限公司 | Glass fiber reinforced polypropylene composite material and preparation method thereof |
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